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Патент USA US3062750

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3,062,740
Patented Nov. 6, 1962
2.
stable in the presence of these contaminants to substan
tially prevent oil from separating out of the emulsion.
Another object of the invention is to provide an oil
3,062,740
OIL-lN-WATER EMUL§ION DRILLING FLUID
William A. Reddie and Eugene R. Werlein, Houston, Tern,
assignors to Magnet Cove Barium Corporation, Hous
ton, Tern, a corporation of Arkansas
in-water emulsion stabilized with certain surfactants so
that in the presence of clay or shale, the emulsion exhibits
superior ?uid loss characteristics even in the absence of
No Drawing. Filed Apr. 18, 1956, Ser. No. 578,865
33 Claims. (Cl. 252-—8.5)
conventional ?uid loss reducing agents.
Another object is to provide an emulsion well ?uid in
which surfactants are employed to control the ?uid loss
This invention relates to oil-in-water emulsion drilling
?uids which are stable in the presence of anhydrite (cal 10 properties of the ?uid.
Another object of the invention is to provide such
cium sulfate) and salt (sodium chloride) and which ex
hibit superior stability when contaminated with clay
orshale. In one of its aspects, the invention relates to
such drilling ?uids and a method for using the same
in drilling through earthen formations having salt or
anhydrite therein. In another of its aspects, it relates
to a concentrate for preparing such a drilling ?uid.
In some oil producing sections, such as west Texas,
salt or anhydrite layers or stringers are encountered
during the drilling of a well which contaminate the drill
ing mud to such an extent that the treating costs to main
tain conventional rnuds in a usable condition are very
high. In such areas, it has, been common practice to drill
hardshales and limestone with clear water since these
formations do not contribute clay to the drilling ?uid.
This has resulted in excessive wear of bit bearings and
cutters and also in slow drilling rates. To prolong the life
of the bits and increase the drilling rates, it has been
suggested that emulsion muds stabilized with anionic sur
factants be used. Unfortunately, however, the salt and 30
anhydrite contamination of these emulsion muds becomes
so extensive that the anionic surfactants form water
insoluble soaps and the emulsion breaks down. Many
surface-active agents or emulsi?ers, both ionic and non
ionic, have been tried but found to be unsuccessful in
such an environment.
The problem is even further ac
centuated by the presence of shale or clay encountered
by the mud during the drilling operation. Thus, while
a combination of surfactants as' a concentrate which
can be readily added to water and oil to afford a stable
emulsion drilling ?uid.
Another object of the invention is to provide a method
of drilling a well through salt- or anhydrite-containing
formations by which method a superior drilling ?uid is
circulated through the well to afford improved drilling
performance, the fluid comprising an oil-in-water emulsion
stabilized with preselected phenolic surfactants.
In general, the objects of this invention are accom
plished by employing certain phenols which have been
water-solubilized by adding a hydrophilic group thereto.
Various combinations of different of these surfactants,
along with other ingredients, can be employed to achieve
variously desired results, as will ‘be explained in greater
detail below.
'
In accordance with this invention, a preferred formula
for forming the emulsion drilling ?uid comprises the fol
lowing active ingredients.
Ingredient:
I ,
Weight percent
OX-240 (nonylphenol reacted with 12 mols of
ethylene oxide per mol of the nonylphenol)__ 47.5
OX~153 1:2 (still bottoms from nonylphenol
process reacted with 2 weights of ethylene
oxide per weight of still bottoms) ________ __ 47.5
Rosin amine D (a primary amine of abietic
acid)
______________________________ ..
5
a few emulsion systems may seemingly be stable in the 40
This preferred formula (by which term it will be desig
presence of salt or anhydrite, the addition of clay or
nated hereafter) of active ingredients is preferably made
shale causes the emulsions to break down. Thus, the
up as a concentrate by dissolving or dispersing the same
problem is not only one of forming a stable emulsion in
in a suitable solvent. It has‘ been found that ordinary sol
an anhydrite salt system but one which is also stable in
vents, such as diesel oil, mixed aromatic, solvents, etc., are
the presence of shales or clays encountered during the
drilling operation.
It is an object of this invention to provide an oil-in
water emulsion drilling ?uid which is of superior stability
unsatisfactory since one or more of the surfactants crys
tallize from solution to form a gel or thick paste upon
' subjecting the mixture to low temperature such as those
likely to be encountered in ?eld use of the concentrate.
not only in the presence of anhydrite or salt but also
Water, of course, is entirely unsatisfactory. The di?li
when contaminated with shale or clay.
50 culty in providing a satisfactory solvent seems to arise
Another object is to provide a particular one of such
an emulsion drilling ?uid which, when contaminated
with clay or shale, causes or permits such clay or shale,
upon. the emulsion remaining quiescent, to settle to the
bottom in a compact layer instead of ?oating to the
top where it would be di?icult to separate from the drilling
?uid under the in?uence of gravity alone.
I
from the fact that the surfactants, particularly the OX.
153 1:2, are not completely soluble in either oil or water
but instead have a “borderline” solubility in each. It has
been found that benzene and the so-called “diacetone alco
- hol” are satisfactory solvents or mediums for permanently
holding all of these surfactants, particularly the oxyeth
ylated nonylphenol still bottoms, in solution despite low
Another, object of this invention is to provide such
temperatures to which the concentrate may be exposed.
an emulsion drilling ?uid to which certain selected
Diacetone alcohol can be described chemically as an al
emulsi?cation agents or surfactants impart the desired 60 cohol-ketone having the formula 4-hydroxy-4-methyl-2
stability and also afford good “spontaneity” during the
formation of the emulsion. The term “spontaneity” is
pentanone.
Sufficient solvent should be used to render the surfac
tants, some of. which are pasty liquids, fluid at tempera
is formed. For example, when a surfactant is mixed with
tures likely to be encountered in the oil field. For exam
oil and the mixture poured into water, there is good 65 ple, a two-to-one mixture of the- preferred formula and
used as a measure of the ease, with which the emulsion
spontaneity if the surfactant-oil mixture easily disperses
in the water phase with little or no agitation.
Another object of the invention is to provide a stable
oil-in-water emulsion drilling ?uid in which a combina
ion of pre-selected phenolic surfactants is employed to
impart the desired salt, anhydrite and ‘clay resistant pro
perties to the ?uid and which renders the ?uid su?iciently "
solvent is satisfactory. The solution is made by pouring
the surfactants and. solvent together and then heating the
same until a clear solution is obtained.
In making up the drilling ?uids of this invention, a
preferred procedure is to add the surfactants per se, or
a concentrate (solution) thereof to the oil which is to
make up a part of the drilling ?uid. This mixture is then
8,062,740
'
3
added to the water with su?icient stirring to give a uniform
dispersion of the oil throughout the water. The water
phase can be fresh water or that which has already been
contaminated with salt or anhydrite, or both. In any
case, a satisfactory emulsion will be readily formed.
4
I
WATER PHASE
The water phase of the emulsion can vary between
rather wide concentration limits but it is preferred that
it be present in a much larger proportion than is the oil
phase. One reason for this is that less of the relatively
It is greatly preferred that the emulsion be formed be
expensive oil and surfactants are required per barrel of
fore the water phase has become contaminated to any
drilling ?uid. Also, as the water concentration is de
extent with clays or shales. It has been found that more
creased and the oil concentration increased, the additional
stable emulsions result if the emulsions are compounded
‘bene?ts derived from the ?uid become marginal so that
before clay or shale is added rather than after clay or
as a practical matter, the additional cost tends to outweigh
shale has been added. The reason for this distinctive
the added advantages. Thus from a practical standpoint,
phenomenon is not known but it is through that when clay
it is preferred that the water be present in a concentration
or shale is added to the water phase before the emulsion
within the range of 97% to 50% (by volume) of the com
is made, the clay or shale hydrates. The hydrated clay
or shale seems to interfere with the formation of stable 15 bined volume of the oil and water. More preferably, the
Water is present within the range of 95% to 80% of such
emulsions and to reduce their capacity to withstand clay
combined volume. In those cases where a lightweight
contamination without breaking down. On the other
emulsion is desired to combat lost circulation problems,
hand, when clay or shale is added to the emulsion, the clay
the Water concentration is decreased even to 50% or less
or shale does not hydrate nearly as much as it does when
so that lost circulation is prevented even though the oil
added to Water alone. This being so, the emulsion has a
concentration is higher than may be desired from a pure
much greater tolerance towards the clay or shale. Stated
in another manner, emulsions can withstand much greater
ly emulsion standpoint.
concentrations of substantially non-hydrated clay or shale
than hydrated clay or shale before the emulsions break
down.
While preforming the emulsion before bringing in any
clay or shale results in superior emulsions, somewhat bet
As indicated above, the drilling ?uid of this invention
is particularly useful where the drilling is to proceed
through salt or anhydrite, or both, deposits as well as
through hard shale and limestone. It has been found that
the ?uid can be compounded originally from either fresh
ter ?uid loss characteristics are noted when the clay or
water or water which has been contaminated with salt
or anhydrite or both. Thus, in some instances, fresh
shale is hydrated before the emulsion is formed. While
this is true, the difference is usually not excessively great 30 water may be available and, if desired, the emulsion can
be made up with this and then the ?lling proceeded with
and, in any event, ?uid loss control can be achieved by
through the salt and anhydrite formations. On the other
conventional ?uid loss reducing agents.
hand, salt- or anhydrite-contaminated water may be in
In this regard, it has been found that certain surfactants,
the mud pits and this can ‘be used to form the emulsion.
identi?ed hereafter, will in themselves cause a marked re
In many operations, the water phase may have various
duction in ?uid loss when added with oil to a Water base 35
mud. Thus, at least 0.5 lb./bbl. (preferably 1 to 10 lbs./
concentrations of anhydrite therein. These concentrations
bbl.) of these surfactants, along with 5 to 50 volume
may range from a very low ?gure to saturation.
percent of oil based on the volme of the water base mud
can be added to the water base mud to reduce its ?uid loss.
This can be done even when the mud is contaminated with
anyhdrite or salt. The oil can be diesel oil, crude oil or
other types of hydrocarbon oils having medium viscosity
characteristics.
It is also possible to form the emulsion drilling ?uid
by adding the ingredients to the water phase and then
The
?uid of this invention is capable of achieving superior
results with any of these concentrations of anhydrite and,
in some instances, the presence of anhydrite actually in
creases the emulsion ?uid’s resistance to clays or shale.
As indicated above, salt (sodium chloride) may also
contaminate or be present in the ?uid of this invention
without substantial adverse results. However, increasing
the amount of salt present tends to decrease the stability
of the emulsion and its resistance to clay solid contamina
tion. Thus, for example, the addition of salt to systems
cause it tends to form less stable emulsions having a
where the water phase is saturated with anhydrite some
tendency to foam more than when the reverse procedure is
what reduces the clay tolerance of the systems even though
used.
In drilling operations, the drilling ?uid of this invention 50 salt water itself tends to reduce the hydration of clays or
shales. This may be due in part to the fact that salt in
has the ability to increase the rate of drilling as compared
creases the solubility of anhydrite in water, thereby in
with the rate when using water alone as the drilling ?uid.
creasing the amount of inorganic ions present in the sys
bringing in the oil. However, this is not as preferred be
This is evidenced by the cuttings being of larger size when
tem to such an extent as to reduce the e?iciency of the
the emulsion is used than when using water, the cuttings 55 surfactants or emulsi?ers. While salt thus does have a
in the latter case being ?ne and powdery. Also, the bit
deleterious effect upon the emulsions of this invention, it
life is increased since the emulsion serves to lubricate the
is surprising that it has as little effect as it does. For ex
bit much better than water does. Further, not only is the
ample, salt can be present in a concentration substantially
drilling ?uid resistant to clay or shale, but the clay or shale
less than saturation without substantially reducing the
is substantially non-hydrated so that it settles to the bot 60 stability of the emulsions or their resistance to clay. How
tom in a comparatively dense, compact layer when the
ever, as the concentration of the salt proceeds toward
?uid is allowed to remain quiescent. This permits ready
saturation, the clay tolerance is reduced so that with water
separation of the clay or shale drilled up during the drill
saturated with salt and anhydrite, only a pound or two
of clay per barrel of ?uid can be tolerated. According
ing operation so that the ?uid can be recirculated while
carrying a minimum of clay or shale. This feature may 65 ly, where high clay concentrations are to be encountered,
it is desirable to limit the salt concentration to be sub
be better appreciated when it is understood that other
stantially less than saturation. As will be seen hereafter,
surfactants, when substituted for those of this invention,
shales, as distinguished from clays, generally have less
result in emulsions in which there occurs hydration of the
adverse effect on the emulsion ?uids than do many types
clay which makes it ?uffy so that it tends to rise to the
70 of clays. Accordingly, higher salt concentrations can be
top and, in some cases, the emulsion itself breaks.
’
tolerated with shales than with clays. The water phase
Although speci?c materials and concentrations are
of this invention, insofar as anhydrite is concerned, can
named above, it has been found that some latitude is pos
contain enough anhydrite to be between ten percent
sible with respect thereto. This is discussed in the do
( 10%) and one hundred percent ( 100%) saturated there
tailed description of this invention which follows.
75 with and usually will be substantially (50 to 100%) saw
.
spear-so
5
Exemplary of this class of alkyl phenolic surfactants
rated.‘ As to salt, the water can contain from zero to
is nonylphenol which has been reacted with an amount
saturation amounts thereof and usually will contain at
least one percent (1%) of salt by weight of the water.
Of course, a typical water will contain both of these
materials.
of ethylene oxide selected from the range of from eight
to ?fty mols of ethylene oxide per mol of nonylphenol.
One such surfactant averaging 12 mols of ethylene oxide
'
per mol of nonylphenol is sold under the trade name
SURFACTANTS
Surfactants for Imparting Clay Tolerance
OX-240. In making this surfactant, propylene is polym
erized to provide a polymer containing a very high per
centage of the nine-carbon chain trimer. This trimer is
then reacted with phenol in the presence of a catalyst,
such as sulfuric acid or boron tri?uoride. There results
a mixture of alkylated phenols which is distilled to pro
In general, it has been found that different classes of
surfactants vary widely in each class’s ability to impart
clay tolerance to oil-in-water emulsions, particularly in the
presence of anhydrite or salt. Further, it has been found
duce an overhead product comprising nonylphenol. The
that the class of surfactants which imparts this superior
clay tolerance will also form superior emulsions even in
the absence of clay. However, clay or shale will always
be encountered in a drilling operation and the emulsions
nonyl group is a branched chain such as a 3,4,5 methyl
hexyl group. Whether or not the nonyl group is straight
or branched chain does not seem to affect this invention.
The separation of the nonylphenol from the other prod
will effectively hinder its hydration.
ucts is conducted at a temperature of at 200° C. and at a
vacuum of 15 to 30 mm. There results a still bottoms
In practice it has been found that a class of surfactants,
comprising certain phenolic compounds which have been
reacted with hydrophilic groups, are satisfactory to stabi 20 which will be discussed in detail below.
The nonylphenol thus separated is then reacted with
lize and impart clay tolerance to an emulsion of the type
ethylene oxide in the presence of suitable catalyst, the
containing one or both of salt and anhydrite. It is pre
amount of ethylene oxide present being controlled so that
ferred to select the surfactant, or mixtures thereof, from
the reaction product, on the average, has a desired amount
the class comprising:
(a) Phenol~oxyalkylene \adduct where about 30 mols of
the oxyalkylene are present per mol of phenol;
25
number of groups results in a surfactant too oleophilic
to satisfactorily stabilize the emulsion. In addition to
(b) Monoalkylphenol- and polyalkylphenol-oxyalkylene
adducts, and admixtures thereof such as certain still
bottoms, where the alkyl groups are of certain chain
ethylene oxide or oxyethylene, other oxyalkylene groups
as oxypropylene can be employed as well as mixtures of
length and the amount of oxyalkylene adducted is
enough to render the surfactant molecule sufficiently
water-soluble that it will migrate to the oil-water in
terface;
-
different oxyalkylenes.
Alkylphenols other than nonylphenol can be made and
treated with oxyalkylene in the manner described above.
0 Among the other monoalkylphenols which may be ad
.
(c) Sulfonated alkylphenol-oxyalkylene adduots likewise
ducted with oxyalkylene (ethylene or propylene oxide)
containing an amount of oxyalkylene to cause migra
tic-n to- the oil-water interface; and
so that the adduct will increase the clay tolerance of and
stabilize the oil-in-water emulsions of this invention are,
(d) Higher molecular weight naphthenic acid-oxyalkyl
by way of example, amylphenol, butylphenol, hexylphe
eue adducts.
Taking up the surfactants by the sub-classes set out
above, the phenol-30-mol oxyalkylene adduct can be rep
resented by the formula:
Ooumnn
of ethylene oxide reacted therewith; that is, an amount
selected from the range of eight to ?fty mols of ethylene
oxide per mol of nonylphenol. The addition of a lesser
40
nol, octylphenol, dodecylphenol and he like. While most
of these phenols are produced in the ortho and para forms
the metal forms are also useful. Also, the alkyl chains
can ‘be straight or branched so as to include the sec- and
tert-forms such as secondary butylphenol, tertiary butyl
phenol, tertiary octylphenol and the like.
As explained above, the alkylate from the reaction of
(I)
phenol with an alkylene is distilled to yield an alkylphenol
where R20 is an ethylene oxide or, less preferably, a
overhead product and a still bottoms. The still bottoms
propylene oxide group and n is at least 28 and preferably
generally comprises a mixture of alkylphenol and dialkyl
is 30. The compound can be prepared in the same man
phenol and in some instances will also include a higher
ner as described below for reacting nonylphenol with 50 boiling residue which may contain polymerized phenols,
ethylene oxide.
_
high boiling alkylates of phenols, complex benzene com
As to the second sub-class broadly identified above,
pounds, and the like. The still bottoms from a nonyl
the monoalkylphenol-oxyalkylene adducts can be rep
phenol process will usually contain from about 15% to
resented by the formula:
55 about 30% of nonylphenol with the balance being dinonyl
phenol and residue. The residue may vary from less than
Q0 (1110) .3
R1
1% to as high as 20%.
To provide another surfactant useful in accordance with
thisinvention, the still bottoms from the alkylphenol sep
(11)
where R1 is an alkyl group connected to the phenylene 60 aration step can be reacted with an oxyalkylene, such as
oxyethylene or oxypropylene to increase its water solu
group and having from 4 to 14, preferably 8 to 12, car
bility. However, in this case, a larger amount of the oxy
bon atoms, R20 is an oxyalkylene such as oxyethylene or
ethylene is preferably used than in the case of the alkyl
oxypropylene, and n is an integer in the range of. 6 to 50.
It is preferred that n be of increasing value as R1 1ncreases
phenol discussed above since the phenolic groups, con
from 4 to 14 and preferably it should be about 20 to 30.
sidered as a whole, have a higher average content of hydro
Thus, a should be large enough, compared with the num
phobic alkyl groups connected thereto than does theaLkyl
ber of carbon atoms in R1, that enough water solubility is
phenol. Thus, it is preferred that the amount of oxyalkyl
imparted to the surfactant that it will migrate to the 011
ene reacted be in the range of 2 to 4, preferably 3 to 4,
water interfacev Further, a usually should be made larger
weights per Weight of still bottoms. In the most preferred
for oxypropylene than for oxyethylene. It will ‘be ap 70 forms of this surfactant, the oxyalkylene will be present
preciated that in any given mass of surfactant, different
within the upper part of the above ranges. Here again,
molecules of the alkylphenol my have different numbers
oxyethylene is preferred although oxypropylene can be
of R20 groups attached thereto so that 11 here is really
the average number of R20 groups for a large number
of alkylphenol molecules.
employed if desired.
75
The resulting adduct comprises a mixture of such
3,062,740
7
8
monoalkylphenol adduct, of the type above discussed, and
Such a mixture has, in a typical production sample, the
a polyalkylphenol adduct which can have the formula
following properties:
Rl
{Dounonn
R3
Average molecular weight ___________________ __ 140
Apparent speci?c gravity _____________________ __ 1.03
Boiling range (ASTM D-850):
IBP
(III)
where R1 and R3 are alkyl groups each having 4 to 14
carbon atoms and having a total in all such groups of 8
___
__
1%
1O
to 28 carbon atoms, n is an integer and R20 is an oxy
° C__ 240
° C__ 242
5% _____________________________ __° C__ 245
50% ____________________________ __° C__ 250
95% ____________________________ __° C__ 270
DP _____________________________ __° C__ 280
Refractive index at 25° C. 1.543.
alkylene group. In many instances, R1 and R3 will have
equal numbers of carbon atoms. Of course, n is selected 15
In addition to the still bottoms and alkylphenol-oxy
so that the total weight of oxyalkylene reacted with the
alkylene surfactants described above, it has been found
still bottoms (total reacted with the dialkyl- and mono
alkylphenols) is within the above weight range and in
that sulfonated alkylphenol-alkoxylene adducts have a
marked ability to impart tolerance of oil~in-water emul
creases within such range as R1 and R3 increase in their
total carbon atom content. A particularly preferred ad
sions toward clay solids. Except that they are more ex
duct is nonylphenol still bottoms adducted with 3 weights
of ethylene oxide per weight of still bottoms. It will be
understood that the still bottoms adducts usable in this
pensive that the above discussed nonylphenol and dinonyl
phenol surfactants, they would be preferred. Asian ex
manufacture of alkylphenols of the type discussed with
reacting the nonylphenol with ethylene oxide and there
after reacting the’ resulting adduct with sulfamic acid
ample of this class of compounds may be mentioned the
ammonium salt of a sulfonated ethylene oxide adduct
invention are not limited to the nonylphenol still bottoms
adducts but can comprise other adducts derived from the 25 with nonylphenol. Such a compound can be made by
reference to Formula II above. In each such instance,
the still bottoms can be derived by distilling the alkylate
(amino acid sul?te). This compound can have the fol
lowing chemical formula:
derived from the alkylation of phenol with a selected
alkylene or equivalent meeting the de?nition of R1 in 30
Formula II. The still bottoms can then be adducted
with oxyalkylene as described above with respect to nonyl
phenol. Thus, there can be adducts of butylphenol still
bottoms, hexylphenol still bottoms, octylphenol still bot
toms, dodecylphenol still bottoms and the like. In some 35 Another method of making the compound is to react the
ethylene oxide-nonylphenol adduct with sulfur trioxide
cases, the percent of the monoalkylphenol present in the
to form the sulfonic acid derivative. This derivative can
still bottoms may vary from the 15 to 30 percent range
then be neutralized with an amine to form the amine
stated above.
derivative or with caustic soda or ammonia, or other base,
-In addition to mixtures of mono- and polyalkylphenols
as above discussed, polyalkylphenol-oxyalkylene adducts 40 to form the corresponding derivatives.
Surfactants in this general class can be represented by
the formula:
the following general formula:
may be used alone. Representative of such compounds is
R:
45
CD0 (moms
R;
(I V)
where R1 and R3 are alkyl groups each having at least
one carbon atom but together having from 3 to 28 car
bon atoms, R20 is an ethylene or propylene oxide group
@o (mmnsoax
(V)
where R; is one or more alkyl groups containing a total
of 6 to 14 carbon atoms, R20 is an oxyalkylene group
selected from the class comprising oxyethylene and oxy
propylene, n is an integer having a value in the range of 4
to 30 and X is a cation such as ammonium, sodium, potas
sium, amine, etc. Examples of this class of surfactants
and n is an integer in the range of 12 to 50. R1 and R3
are the sulfonated alkoxylene adducts of hexylphenol,
can be separate alkyl groups or they can be a single group
octylphenol, heptylphenol, dodecylphenol, methylhexyl
55
connected as a ring to adjacent phenylene carbon atoms
phenol, ethylnonylphenol, propylbutylphenol, propyloctyl
as in the indanols. Here again, n should increase as the
phenol and the like.
total carbon atoms in R1 and R3 increase but in most in
stances, a value of n in the range of 20 to 40 _will be
The surfactants conforming to the above general for
mula can be made by the same process as described with
satisfactory. Exemplary of this sub-class of compounds
respect to the ammonium salt of sulfonated nonylphenol
are the oxyalkylene adducts of dibutylphenol, diamylphe 60 ethylene oxide adduct.
nol, dioctylphenol, dinonylphenol, didodecyl phenol and
When this sulfonated surfactant is employed in systems
the like, as well as mixed alkyl group phenols such as
having relatively low clay concentrations, e.g. below seven
lbutylamylphenol, methylnonylphenol, ethylhexylphenol,
pounds per barrel, the amount of oxyalkylene employed
butylnonylphenols, octyldodecylphenols, and the like. Also
can be within the range of 4 to 30 mols per mol of the
falling in this class are the “high boiling phenols” which 65 sulfonated alkylpheno . However, when higher clay con
are a mixture of alkyl phenols, a predominant portion of
which are meta-substituted and also including
Percent
4-indanol _______________________________ __
centrations, e.g. above ?ve pounds per barrel, are to be
used, the amount of oxyalkylene should generally be in the
lower part of this range, say, from 4 to 12 mols per mol
of the sulfonated alkylphenol-oxyalkylene adduct. It has
15
15 70 been observed that this compound becomes more e?icient
for its intended purpose as the amount of oxyalkylene is
3-methyl 5~ethyl phenol ___________________ __
l0
reduced through the above range. Thus, the 4-mol adduct
n-Propyl phenols
5.10
of sulfonated nonylphenol is more efn‘cient in causing the
Other alkyl phenols ______________________ __ 1 50-55
emulsion to be clay tolerant than is a IO-mol adduct.
1 Mostly meta substituted.
75 This is in contradistinction to the nonyl and still bottoms
S-indanol
3,062,740
‘in
(A
adducts. In these it has been found that their efficiency
increases as the amount of oxyalkylene is increased.
range of 10 to 50, preferably 30 to 50, Weight percent
of the total active surfactants present. Increasing the
Another sub-class of surfactants for increasing the clay
amount beyond this range tends to cause oil to separate
from the emulsion.
tolerance of the emulsions of this invention are the oXy
alkylene adducts of high molecular weight naphthenic
Corrosion-Inhibiting Surfactants
acids. These acids have one carboxyl group per molecule
and contain two to ?ve saturated interconnected rings per
molecule. They can occur as many possible types such as
It has been found that when emulsions of the type
described are used in the ?eld, severe corrosion can re
sult to bits and other drilling equipment. To inhibit
this, a cationic surfactant. having corrosion-inhibiting
powers is added to the emulsion. In the preferred for
mula, Rosin Amine D is used for this purpose. This
compound is described as the primary amine of abietic
acid, the latter being derived from tall oil. It is thought
15 to have the following formula:
10
CH3 (lIlHzNHa
These acids should have a molecular weight in the
range of 300 to 350 and an acid number of 160 to 190‘.
They can include a benzene ring and mixture of 5 and
H3O ‘
6 carbon atom saturated rings. The oxyalkylene groups
substitute in the hydroxyl group of the carboxyl radical 25
similar to the phenols described above. The amount of
oxyalkylene should be from 15 to 50 mols per mol of
naphthenic acid.
Surfactants for Imparting spontaneity
CH3
oga
CH3
(VII)
The amount of the corrosion-inhibiting surfactant
30 should be in the range of 2% to 10% by weight of the
In order to improve the appearance of the emulsions
as they are formed, and also the ease with which they
,are formed, it is sometimes desirable to add a surfactant
total surfactants present.
The amount of clay-tolerance imparting surfactants
vwill, of course, be in the range of 88 to 40, preferably
68 to 40, weight percent of the total active surfactants.
having the property of causing the emulsions to be easily
With surfactant concentrations in the above range,
formed even though it, in itself, is not particularly effec 35
the total amount of surfactants employed to form the
tive in stabilizing the same. Thus, as a general rule, the
oil-in-water emulsion should be at least 3 and prefer
class of surfactants described above as imparting clay
ably at least 5 weight percent of the oil phase employed.
tolerance to emulsions do not have as much “spon
Higher concentrations than these minimums do not harm
taneity” as may be desired. It has been found that the
surfactants of the above described sub-classes but hav 11-0 the emulsions but too high concentrations are uneco
ing less oxyalkylene adducted therewith will generally
nomical.
impart good spontaneity when used with the clay-toler
As used in this speci?cation and claims, an emulsion
ance imparting surfactants.
In a sense then, the more
oil soluble surfactants are used to improve spontaneity.
Among the compounds which can be used for this pur
pose are:
(1) The dialkylphenol-oxyethylene adducts represented
by the formula
formed of a “major” amount of water and a “minor”
amount of oil means that both water and oil are present
with the concentration of the water being 50 percent or
greater than the oil being 50 percent or less of the com
bined water-oil volume. Also, when it is stated that water,
oil or a water-oil emulsion contains one or both of sodium
chloride (salt) or calcium sulfate (anhydrite), it is meant
that such compounds are present in an amount which is
signi?cant under the conditions which a drilling mud
is used. Further, where reference is made to oxyal
kylene herein, ethylene oxide (oxyethylene), propylene
Ra
when R1, R3 and R20 are as above described for Formula
IV and n is an integer having a value in the range of
10 to 14. Thus, dinonylphenols which have been re
acted with about 10 to 14 mols of ethylene oxide per
oxide (oxypropylene) or admixtures thereof are meant
55 although it is possible to use higher alkyl oxides by using
more of them to form the adduct.
Illustrative Data
To demonstrate the e?ect of varying the concentrations
mol of dinonylphenol are satisfactory. Other examples 60 of different surfactants, the tests reported in Table I
were run. For these tests, the various surfactants were
of the phenolic radical are named above in respect of
combined in the weight percentages indicated and a con
Formula IV.
centrate made by causing a crude temporary dispersion
(2) More preferably, still bottoms from an alkylphenol
of the surfactants in an aromatic hydrocarbon. The
producing process as above described which have been
recated with about 1 to 2 weights of oxyalkylene, such 65 amount of hydrocarbon used was suf?cient that its weight
constituted 30% of the ?nal concentrate. One pound
as ethylene oxide or propylene oxide, per weight of
per
barrel of the concentrate was then mixed with enough
still bottoms. Such surfactants will impart even greater
diesel oil that when the oil was added to water, its
spontaneity than the dialkylphenol type. Satisfactory
volume constituted 8% of the total oil-water volume.
surfactants of this type are OX-l53 1:1 and OX-l53
1:2 which are still bottoms derived from a nonylphenol 70 As indicated in the table, various types of water were
used. In the ?rst column of results, 4% of sodium
process are above described reacted respectively with l
chloride by Weight of the water was added thereto, along
and 2 weights of ethylene oxide per weight of still bot
with su?icient calcium sulfate to saturate the same. In
toms. OX-l53 1:2 is preferred.
the second column the salt was omitted and the water
The amount of this type of surfactant (spontaneity
producing) which can be employed should be in the 75 saturated with calcium sulfate.
TABLE I
Surfactants, percent 1
OX-24O
(Di-1153
:
O2§~l53
:2
AdNdléct
—
.............. __
90
______ _______ -9O
45
______ ._
.. _
. __
6126
5
5
5
5
45
5
RAD spontaneity
Emulsion Foam O11
5
5
5
5
0
7.0
T
2.0
5
0
...... __
42. 5
____.
___
T
42. 5
42.5
.._...
.__
1.0
40
_......_
_____ ._ . _ _ ___
4% salt, sat. anhydrito water
85
. . . . . . ..
7
3
. .. ..._.
. . _ ..
-__
._-_.-..
40
-__-_
.__
._-_-
._-
85
Good ...... __
_.-._
Very good___
Sat. anhydrlte water
spontaneity
Emulsion
Very good .... -.
o__.__--
S
S
Very weak._
VS
Very good...
8
T
T
8. 0
'1‘
Fresh water
Foam
Oil
VS
S
S
VU
S
S
S
S
S
0
4. 0
T
0.2
T
0
T
T
T
1.5
S
T
Spontaneity
Emulsion
Very good ...... _-
Foam
Oil
S
VS
S
U
S
S
S
S
S
S
T
T
0
T
T
0
0
0
0
T
S
P
1OX-—24O, OX-153 l : 1, and OX-153 1 : 2 are as identi?ed above. Adduct N-2 is nonyl
phenol adducted with 2 mole of ethylene oxide per mol of nonylphenol.
At this point, the test procedures employed will be ex~
true where the water phase contained both salt and an
plained. The observations of “spontaneity” indicate the
hydrite. Emulsions containing high percentages of
ease with which the diesel oil-surfactant mix spread
OX-l53 1:2 had the same tendency but to a markedly
less extent. High concentrations of OX~240 resulted in
through the water when poured thereinto.
if the spread
ing was rapid and there was little tendency for the oil to
segregate from the water after it was poured thereinto,
the spontaneity was considered to be good. If the oil
tended to rapidly rise to the surface of the water as a
separate layer and very little emulsion was formed when
the oil was poured into the water, the spontaneity was con
sidered to be poor. Other degrees of spontaneity were
noted as fair or very good.
Under the columns labeled “Emulsion,” the appearance
of the emulsion was noted.
Those emulsions which had
a rich creamy appearance were noted as good or very
good. Emulsions which appeared thin were termed weak
or very weak, depending upon their appearance. Emul
sions of intermediate appearance were, of course, labeled
fair.
Under the column labeled “Foam,” the amount of foam
appearing on the emulsion after agitation on a Hamilton
Beach mixer for 5 minutes at 60 volts was noted. This
measurement was made by having one barrel equivalent
(350 ml.) of the emulsion in a one-quart Kerr Mason
jar and then beating as above noted. The foam was meas
ured and its height reported as a percentage of the height
stable emulsions insofar as oil break-out was concerned.
It will also be noted that when OX~240 and OX-l53 1:1
were used in equal proportions, the high concentration
of the latter also caused oil to break out. This is not true
where OX-153 1:2 was substituted for the OX-153 1:1.
Accordingly, it can be concluded that OX-l53 1:1 has a
deleterious effect upon emulsions insofar as oil break
out is concerned. It will also be noted that emulsions
with high concentrations of OX~240 were somewhat lack
ing in spontaneity. However, the spontaneity was im
proved by the addition of Adduct N—-2, OX-l53 1:1 or
more preferably OX-153 1:2.
A series of tests similar to those reported in Table I
were run but using two pounds per barrel of the various
surfactant-solvent mixes and in general the results were
the same except that the emulsions containing high con
centrations of OX-240 exhibited greater clay tolerance
than at low concentrations, whereas those wtih high con
centrations of 0X—l53 1:1 did not appreciably change in
clay tolerance. Emulsions high in OX-l53 1:2 did not
appreciably change in clay tolerance in the salt- anhy
drite systems but did increase somewhat in the anhydrite
of liquid in the jar. In Table I the following notations
60 and fresh-water systems.
are used:
“S”--Foam height was 30% to 40% of liquid height.
“U”—Foam height was 40% to 50% of liquid height.
“VS”—Foam height was less than 30% of liquid height.
“VU”--Foam height was greater than 50% of liquid
height.
In the tests reported in Table I, a low yield, calcium
montmorillonite type of clay was used. This clay had a
particularly severe effect upon the emulsions and to demon
strate the less severe effect of shales expected to be en
65 countered in the drilling of wells, there was secured a
sample of shale from a well in which the drilling ?uids
of this invention would be used.
Tests were then run with
Under the column labeled “Oil,” the amount of oil
various surfactants to determine the e?ect of shale upon
which broke free from the emulsion after standing for 24
emulsions made therefrom. These tests are reported in
hours is reported. If only a thin ?lm was reported, the 70 Table II. In the tests, the water phase consisted of water
Amounts greater
saturated with calcium sulfate and containing 4% by
than this were measured in percentage of total volume of
the emulsion. Referring to Table I, it will be seen that
when the concentration of OX-153 1:1 was high, consid
amount of was reported as a trace (T).
Weight of sodium chloride. Diesel oil in an amount su?i
cient to provide 8% of the volume of water was added
to the water, which had previously been treated with one
erable oil broke from the emulsion, and this is particularly 75 half pound per barrel of surfactant. The mixture was
3,062,740
13
14
stirred for ?ve minutes at 60 volts on a'I-Iamilton Beach
termed “emulsion.” Since the cream is a rich emulsion
mixer and then allowed to stand for ?ve minutes, after
which observations were made. However, in the instance
reported in the third column, the observation was made
after 24 hours of standing. Increasing amounts of the
?nely ground shale were added as indicated in the table.
and the “emulsion” is a leaner emulsion, the height of the
cream layer is a measure of the stability of the emulsion.
.In other words, the salt-anhydrite water is much heavier
than 'oil and the difference in gravity is such that oil~
rich emulsion tends to rise to the top of the oil-lean
TABLE II
No shale
Surfactant
Foam Cream
10 lb./bbl. shale
Oil
Emul.
Foam Cream
Oil
Emul- CtO.B.
sion
1A5”
None
sion
0X-191 _______________________ __
946”
50% OX—372,50% 011-374--.-"
$46”
346” _._do___ -_-do___
1%6”
316” __.do._. __.do.._
946”
0X-240 _______________________ __
$40”
$46” -__do_-_-__do_-_
Good
$45”
6"
M6"
5/6” ___do___ __-do_--
e46"
10 lb./bb1. shale-24 hrs.
Surfactant
None
Good
12 lb./bbl. shale
Foam Cream Emul- 0.0.13. Foam Cream Emul- 0.0.13.
S1011
346"
‘Va’’
1}’15”
346”
$10!].
Good
?e"
916” .__do___
éie" --_do___
$46”
a”
Me”
1%6”
Me"
14 lb./bbl. shale
Surfactant
.
0X-191 _______________________ _OX—3"2, 50
OX-374-
__
OI%—240_-:._-__‘.7€ ------------- -.
g'fs”
Good
$ia"
Clay ?occed to top
%e”
0X-191 ______________ __
OX-374.
ilfs”
0X-240 ______________ __
Cream Emul- 0.0.13. Foam
sion
3A6”
sis"
‘Mo”
.
Cream
Oil
aAu”
%e”
Good
‘340"
%6”
Me"
None
V15"
GOOd
?e"
3/15"
Mo"
None
_
O11
Emul- C.O.B.
sion
_
Fair-.-
é/rs"
Good
{146"
24 l'o.lbbl. shale
-
.
Emul- C.O.B. Foam Cream
Flocc<dclay present
-
3A5"
Good
tie” Good
20 lb./bbl. shale
S1011
50% OX-372, 50%
$66”
?e”
sion
3405"
Foam Cream
Me”
Cream Emul- 0.0.13.
22 lb./bbl. shale
Surfactant
_
sion
18 lb./bbl. shale
Foam
Good
Foam Cream Emul- C.O.B. Foam
%6”
Surfactant
%&”
Me" -__do-__
%6” ___do___
161b./bbl. Shale
Ma"! ?io” I Good I 546” $40"
50
$48"
..
_
O11
,
Emul- C.0.B.
S1011
$46”
_
Me”
None
,
Fan-m
5,15”
Clay ?occed to top and bottom
No'rr:.—-OX—191 is nonylpheuol reacted with 30 mols of ethylene oxide, 0X-372 is a dice henzyl chloride
quaternary reported to have the formula
C1
Where R is the alkyl groups of coco fatty acids (mixtures of 10_, 12 and 14 carbon. atom alkyl groups);
0X~374 is a fatty acid fraction derived from tall oil (less than 1% rosm acid) adducted with 30 mols of ethylene
oxide.
In this table, the height of foam and cream are reported
in inches. In making these measurements, one barrel
“emulsion.” The term “C.O.B.” is the measurement of
separate phases would occur in most instances. The top
most phase was foam. Below this foam was a layer
and the OX-24O showed excellent tolerance toward shale
whereas the mixture of OX-372 and —374 showed a much
lesser tolerance.
As indicated above, the amount of oxyalkylenes added
the amount of clay (or shale) settling to the bottom of
equivalent of the emulsion (350 cc.) was poured into a 70 the Mason jar. All measurements were taken after the
emulsion had stood for 24 hours.
one-quart Kerr Mason jar and the foam and cream meas
From the table it will be observed that the 0X-19l
ured. After standing, it was observed that at least three
' termed “cream.” It comprised a rich layer of emulsion
which had separated from the next lower phase, which was
3,062,740
15
to the phenolic radical determines the water-solubility of
the resulting compound. This has an effect upon the abil
ity of emulsions formed therefrom to withstand con
tamination by clay. This is demonstrated in Table III.
For the ?rst three surfactants, 2 1bs.'/bb1. of the surfactant
were added to enough diesel oil to yield an emulsion of
8% oil. The mixture was then added to water saturated
ity to clay. While from a purely clay resistable stand
point, it would be preferable to use nonylphenols having
20 to 30 mols of ethylene oxide reacted therewith, such
cause more foaming than those with lesser amounts of
the oxide. As a result, the lower alkoxy compounds will
be used where clay contamination is not expected to
exceed the “limit” for the particular compound.
with anhydrite and containing 4% by weight of salt. For
The test results re?ected in Table IV further demon
the last three surfactants, the procedure was reversed by
strate the effect of adding di?erent amounts of ethylene
adding the surfactant to the water and then bringing in 10 oxide to phenolic radicals. In these tests, 1lb./bbl. of
the oil.
surfactant was dispersed in diesel oil, after which the mix
TABLE III
10 lb./bbl. clay
Surfac-
Foam
Cream
Oil
taut l
15 Ib./bbl. clay
Emu]!
17 lb./bbl. clay
20 lb./bbl. clay
0.0.13.
sion
8 mol ____ -_
0
0
10 mol...--
0
He”
____ ..
Good _
C.F.'I‘.’I‘-.
C.F.'I‘.'I‘
.... .- .__do .-
Yes _____ .-
Clay ?oeced—Emul
_
_
sion fair.
12 mol.._-.
0
?e"
15 mol___-.
0
94a” .... .. ...do._- Yes.._._.. C.O.B.'—Fair emulsion- C.O.B.—-Fair emulsion__.- Clay ?o§0§d—2” C.O.B., water
do
Yes.._.__. Clay ?occed—-No emul
20 m0].....
Bio”
sion.
separa e .
30 mol_.... —1” Total
945”
____ _.
Fair.--
do
Yes _____ __ _
do
____ do
Yes _____ __
dn
____ dn
Do.
COR-Not ?occed, fair emul
s on.
It will be observed that as the amount of ethylene oxide
added is increased, the emulsion shows increased resistiv
ture was added to the water.
The amount used was
enough to yield an 8% oil emulsion.
TABLE IV
Fresh Water
N0 clay
3 lb./bbl. clay
Sn?actantI
_
spontaneity
Emulsion
Foamz Cream7 Oil 1
Foam Cream
0!]
Ernui- 0.0.13.
sion
2
2
3
2
1.5
1
2
3
6
6
1
(JFT'I‘ 3
CF’I‘T 1’
(‘FT’I‘ %
'1‘
T
1A5"
94a”
He”
4A0"
0
0
0
T
T
T
Mo”
éio”
0
7 lb./bbl. clay
Surfactant
Foam
Cream
O11
Emul- G O B
Foam
Cream
Oil
Emul- C.O.B.
sion
Emulsion very weak
”
OX-153 1:3 ___________ __
i "
SIOD
15%” tclay on
0
Fair...
0P
gig”
34g"
0 Good-_
%a"
aAu”
M5”
3A0"
540”
0 Good_.
$16"
0
'1‘ _._d0.._
%6"
1,40”
Ms"
0 "-60---
'Hu"
345"
Me”
'1‘ ..-d0-._
i’yio”
9hr”
I/ui”
T
?e"
9 lb./bbl. clay
Surfactant
Foam
Cream
Oil
Clay semi-?occed
fin
1540”
11 lb./bbl. clay
Emul- 0.0.13. Foam
Cream
Oil
Emul- 0.0.13.
sion
Clay semi-?occed
.346”
sion
ate”
Clay semi-?oeced
'7‘io"
CFTT & B i
.
CF'I‘T & B i
............... .
?e” i Me" I
0 | Fair... 9%"
CFTBl
3,062,740
18
17
TABLE IV——Continued
Water Saturated With Anhydrite
No clay
Surfactant
Sponta- Emulneity
sion
3 lb lbbl. clay
Foam
Cream
Oil
Foam
Cream
Fair.-.
___do__Good
None
2
2
7
15
O
1
5
O
6
6
T
7
Good
15
5 '
T
"
Fair___
14
8
T
1/16”
Good
10
4
T _
3/16”
Foam
Cream
Oil
O
me"
0
2/16”
2/16”
3/16"
0
T
T
Foam
Cream
-
Fair--
0
Good
7 1b./bbl. clay
Good
Cream
Oil
Emul- C.O.B.
sion
'1 """" " CFTT3
Fair___
Good
16"
'2/16”
1/16”
2/16”
None
3/16”
0
'1‘
T
______ __
Fair___
Good
3/16”
3/16”
11 lbJbbl. clay
‘
Oil
Good
T
0
9 lbJbbl. clay
Surfactant
Weak,
___do___
Good
Weak_
T
3/16”
Emul- C.O.B. Foam
sion
3/16”
Emul- C.O.B.
sion
CF'I‘T 3
CFT'I‘ 3
CFTT 3
CFTT & B 4
51b./bbl. clay
Surfactant
Oil
VEmul- C.O.B. Foam
sion
Cream
Oil
Emul- C.O.B.
sion
0X-153 1 9
OX-240 ______________ __
OX-153 1:3 ___________ __
CFTT & B 4
1/1 ’
Fair___
1/16”|
0 ___do___
2/16”
CFTT ‘
None
______ __
4% Salt Water Saturated With Anhydrite
No clay
Surfactant
spontaneity
3 lbJbbl. clay
Emul- Foam2 Cream2
Oil 1
\
Foam Cream
Oil
Emul‘ C.O.B.
s1on
S1011
Poor..
Fair___
6
2
2
1
Good ..
_ None-
10
6
0
0
1
8
Good ;
16
7
'1‘
Fair---
14
7
T
M
Good _
8
5
'l‘
at
OX~153 1:3---"
7
7
1A
5 lb./bbl. clay
Surfactant
Foam
Cream
Oil
7 lb./bbl. clay
Emul- C.O.B.
sion
Foam
Cream
_ ‘Weak.
Oil
Emul- 0.0.3.
sion
-
T
Fair---
ilia”
0
Good _
~7io”
CFTT & B
3716”
Me”
Poor" ______ __
0
Good -
3A6"
9 lb./bbl. clay
Surfactant
Foam
Cream
Oil
Emulsion
C.O.B.
DP-?
DP-Q
DP-12
P
OX-15311 2
OX-24?
OX—153:1:3 ______________ -_
CFTT
None ______________________ __
l DP-(i, —9, and. —12 are diuonylphenols addueted with 6, 9 and 12 mols of ethylene oxide respectively; NP is
nonylphenol; OX-153 1:3 is the same as 0 X-153 1:2 except that 3 weights of ethylene oxide are reacted with each
weight of still bottoms.
2 Values taken as mill iliters in a 100 ml. sample of emulsion ?uid including cream, foam and oil.
3 Clay ?occed to top.
4 Clay ?occed to top and bottom.
6 Clay ?occed to bottom.
From this table it will be seen that the particular di
nonylphenol with 12 mols of ethylene oxide corresponds
to OX~240 except that the formula contains an additional"
nonylphenol-ethylene oxide adducts resulted in emulsions
having substantially no tolerance to clay. Since the di 75 nonyl group, it is thought that the hydrophobic tendencies
8,062,740
‘19
of this surfactant exceed its hydrophilic tendencies to a
degree not permitting it to satisfactorily stabilize the
emulsion. However, it should be noted that nonylphenol
20
was made up into an-emulsion containing 8% of diesel
oil by volume and 92% of water saturated with anhydrite
and containing 4% by weight of salt.
TABLE V
No elay
5 lb./bbl. clay
Surfactant l
Foam, Cream,
per-
cent 2
22
per-
cent 2
8
Oil
T
Foam Cream,
Emulsion
in.
Good ________ _.
Ma
Oil
Mu
.O.B.,
Emulsion
in.
T
3A0
39
7
T
Mo
‘31 a
T
ti o
44
6
T
.._..de ....... __
94o
§4o
T
Me
65
4
0
Fair to weak_-
‘Mu
§iu
0
‘its
0
Fair ......... ..
28
8
Fair-
in.
Me
‘340
0
.__-- 0 ....... -.
37
8
0
§ia
Me
0
Fair to good___
%;
40
59
6
6
T
T
340
He
§4e
?e
Mo __.__d0 ....... -T
Fair_________ ..
"As
Ma
8 lb fbhl. clay
Surfac
‘W:
11 lb./bbl. clay
tant 1
Foam, Cream,
in.
in.
DM ____ -_
?e
a/ts
Oil
Me
3/i6
0
3hr
%ie
0
12 1110l____
‘$40
‘$40
Me
$45
0
$40
Me
0
30 IDOL“-
M-l ____ __
M-2.... __
%e
_
Fall‘ ......... --
0
Clay ?oceed
m cream
94s
446
C.O.B , Foam, Cream, Oil
in.
in.
in.
0
4 mol_-__.
8 mol____.
20 moL-.-
Emulsion
Fair to weak_-
Emulsion
(‘FTT
______ __
9As
Ma
Ma
0
§4e
946
‘M6
0 .._._do____.
§ie
%a
Mo
0
946
Fair to good___
5A6
__
$45
Fail‘_________ _.
‘?e
C ["TT & B
Fair ......... __
94o
CFTT & B
Ma Fair to weak._
Mu
Clay semi-?oeced
Fair ......... _.
%@
Clay semi-?occed
0
C.O.B ,
in.
______ __
14 lb./bhl. clay
Surfactant l
Foam, in.
Cream, in.
Oil
Emulsion
C.O.B., in.
H6
§4e
0
5A a
345
“A6
Ma
§io
0
0
5A6
7A6
1 DM is a 67-33 mixture b y weight of OX-240 and aromatic hydrocarbons; 4 mol to 30 mol indicates the am
monium salt of sulfonated nonylphenol having the indicated mols of eth ylene oxide addueted therewith; M-l
is a mixture of 80 % of the 4 mol ammonium salt compound plus 20% of sorbitol esteri?ed with 1.3 mols of tall
oil per mol of sorh itol and having 18 mols of ethylene oxide adducted there with; M-2 is the same except the 8 mol
ammonium salt compound is used instead of the 4 mol.
9 Percent of original liquid height.
per se resulted in emulsions (with fresh water phase only)
From this table, it will be seen that as the amount of
which were superior in their clay tolerance compared (5;, ethylene oxide which is present in the sulfonated com
to the dinonylphenol-ethylene oxide adduct emulsions.
pound is increased, the resistance of the resulting emul
It will also be noted from Table IV that the OX-153
sions to clay is reduced. Best resistance seems to be
1:3 results in emulsions superior to those containing
yielded by the 4 to 8 mol adducts. It will also be seen
OX-153 1:2. Other tests, not reported herein, show that
that the sulfonated compound containing the smaller
OX-l53 1:1 is considerably inferior to either of OX-153
amounts of ethylene oxide is superior to OX-240 in im
1:2 or OX-153 1:3. It is thought that the reason for this
parting clay resistance to emulsions.
is that the increased amount of ethylene oxide added
In Table VI, various phenol adduct surfactants were
to the still bottoms renders the latter more water-soluble
tested in 4% salt water saturated with anhydrite. One
and hence of more e?iciency in the emulsion.
Table V reports results on tests showing the clay toler 70 lb./bbl. of the surfactants was added to enough diesel oil
that when the resulting mixture was added to the water,
ance of the ammonium salt of sulfonated nonylphenol
8% by volume of oil was present. Clay was then added
ethylene oxide adducts to which has been added varying
in increments until the clay ?occed. In each use, an emul~
amounts of ethylene oxide as indicated. In running
sion was formed but the spontaneity was either very poor
these tests, one and a half pounds per barrel of a com
mercial form of this salt (which is 65% active material) 75 (OX-438) or none (all the other surfactants).
3,062,740
22
a mixture of methylphenol, ethylphenol and propylphenol.
The effect of the preferred formula upon the ?uid loss
of emulsions containing shale, with and without a ?uid
loss reducing agent, is shown in Table VIII. The results
TABLE VI
Surfactant
Clay, 1bs./bbl.
Emulsion
Trade
name
Chemical name 1
Amt.
Amt.
added
with
re
quired
no
to
?oecing
?oc
5 in this table were obtained from emulsions containing
30% by volume of diesel oil, water saturated with an
hydrite and containing 900 ppm. of Cl- plus 1.43 lb./bbl.
of the preferred formula. The amount of shale employed
OX—431____
Amylphenol+30 ________ __
5
7
OX—433-___
Resoreinol+30__
0
3
_
021-434.-" Resorcinol+60____-
0
3
050438.... High molecular weight
7
9
naphthenic acid-P30.
OX—444_..- Di-sec-butylphenol+30____
5
7
OX—445.___ Meta-isopropylphenol+30-
0
a3
OX—447_.__ Para-isopropylphenol-i-litl.
0
3
OX—448__-_
0
3
Oresylic acid+30 _______ __
was 15 lb./bbl. and it was obtained from a well in West
10 Texas where salt and anhydrite stringers were encoun
tered. l lb./bbl. of carboxymethyl cellulose (CMC) was
used as indicated. Aging was overnight.
In the Order I mixing, the shale was added to fresh
water and the mixture aged. Then the preferred formula
and oil were added and the emulsion aged. After the
properties had been measured, the CMC was added and
OX—449__-_ Oresylic acid “FF”+30-
O
OX—451____
0
3
0
0
3
3
mixing, the emulsion was ?rst formed and then the shale
Para-cresol-i-{SO _____ __
021-452-..- Cyelohexanol+30_
OX~455____ Catech0l+60_____
3
aged and properties again measured. In the Order II
OX—463____
Beta-naphthol+30_
_
0
3
OX—489____
Aniline-{$0 _____________ __
0
3
added. After this mixture had aged and its properties
OX—490___- Ori6ho-sec-butylphenol+
3 .
7
OX-49l____ Para-sec-butylphenol+30..
5
9 20 measured, CMC was added. In the Order III mixing,
the emulsion was formed and driscose added. After
7
OX—i92____ 2,4,di~tert-butylphenol+
7
9
aging, the properties were measured and then shale
OX~4Q5B__ Ortho-ehlorophenol-i-30___
0
3
added.
OX—496___. Par-)a-tert-butylphenol+
3 .
5
7
OX-497__._ Tris (a methyl benzyl)
5
7
OX—498____ Para-ehlorophenol+30_____
OC—60022__ Meta-aminophenol+30___
OPE—30____ Tert-octylphenol-I-30_____
O
3
3
3
5
5
FB—2688___
FB—2689_-_
Din0nylphen0l+30 _____ __
Dodecylphenol+30... __
_
7
5
9
7
OX—191____
Nonylphenol+30 ________ __ .
7
9
OX-242____
30.
phenol-F30.
Meta~phenol+304 _______ __
0
3
OX—450____ High boiling phenols-P30"
0
33
OX—440____
OX—504..__
0
0
3
3
O
0
0
3
3
3
Ii‘urfuryl alcohol+30 ____ __ _
Orth0-eresol+30 ________ __
OX-505____ Cresylic acid D—11—A+30__
OX—506____ Cresylic acid D—2—B+30__
OX—507__._ Meta-phenol 220+50 4_____
TABLE VIII
Immediate properties
Mixing order
Yield
point
App.
visc.
F.L.
cp.
Yield
point
F.L.
cp.
30
8
39
6
41
25
24
O
22
0
30
20
8
11
3. 3
15.4
4.2
14
5.0
From this table, it can be seen that the surfactants per so
1 Term indicates basic phenol, etc. and the number indicates mols of
ethylene oxide add-noted therewith.
have a marked ability to reduce ?uid loss. Thus, with no
?uid loss agent (CMC) present, the surfactants caused
2 Apnreeiable tree oil broke out upon aging overnight.
3 With this much clay, ?eecing had started but was not great.
a ?uid loss reduction from 37 cc. to 11 cc. after time had
I41 Melta-eresols are reported to be mixtures of methyl-, eth} l- and propyl
p eno s.
been allowed for them to interact with the shale. Also,
better ?uid loss reduction was obtained when the shale
was permitted to hydrate prior to forming the emulsion.
To further demonstrate the ?uid loss reducing charac
teristics of certain surfactants, the tests reported in Table
From the table, it will be seen that short chain alkyl
phenol adducts, such as cresol, do not impart clay toler
ance when adducted with the amount of ethylene oxide
reported in the table.
IX were run. In these tests, 15 lb./bbl. of shale was added
Another series of tests were run in the same manner as
those reported in Table VI.
App.
vise.
Aged properties
to water saturated with anhydrite and containing 900‘
They are reported in
Table VII.
p.p.m. of C1“. The shale-water mixture was then aged
TABLE VII
Surfactant
OX—240 (nonylphenol adduoted with 12 mols
ethylene oxide).
ethylene oxide).
OX-l91 (nonylphenol adducted with 30 mols
ethylene oxide).
OX-377 (phenol adducted with 30 mols
ethylene oxide).
OX-259 (nonylphenol adducted with 20 mols
ethylene oxide).
00-5073L (phenol addueted with 20 mols
ethylene oxide).
OX-372 (meta-phenol adducted with 15 mols
ethylene oxide).
0X-242 (meta-phenol adducted with 30 mols
ethylene oxide).
OC-5073l (phenol adducted with 12 mols
Spontaneity
Foam,
percent
Cream,
percent
of liquid of liquid
height
height
Oil,
percent
liquid
Clay
Emul
sion
3 lb./bbl.
5 lb./bb1.
7 lb./bbl.
9 lb./bb1.
Poor_.__
37
10
0
Good___- 0.0.B._._ (3.0.3.... 0.0.3.... C.F.T.T.
Fair__.__
100
0
8
None
_-_do.___.
50
10
0
Fair._
___do.__._
75
8
___do___..
50
10
None____
112
0
4
Fair..."
112
0
4
None.__.
87
3
0
G.O.B____ 0.033..-- (10.13.... O.F.T.T.
0 ___do_____ C.O.B__.- C.O.l3.___ C.F.T.T_
0 ___do_____ C.O.B_-__ C.O.B____ C.O.B.___ G.F.T.’l‘.
Fair-_-__
overnight. Then the indicated surfactant was added along
It will be seen that phenol adducted with 30 mols of
with enough diesel oil to give an emulsion having 30%
ethylene oxide imparted some clay tolerance to the emul
by volume of oil, the mixture agitated and aged over
sions whereas phenol adducted with 12 or 20 mols of
night. Properties were then measured. CMC was then
ethylene oxide did not. Meta-phenol with 30 mols of
ethylene oxide also failed. Meta-phenol is reported to be 75 added (1 lb./bbl.) and the emulsion aged overnight.
3,062,740
23
24.
TABLE IX
Agent
amount of water substantially saturated with calcium sul
fate and containing at least 1 percent by weight of so
Emulsion without
Emulsion with
CMC
/
Lb./bbl.
App.
EL.
App.
dium chloride, said emulsion being stabilized by at least
one surfactant present in an amount of at least 0.5 pound
per barrel and selected from the group consisting of: (a)
phenol adducted with at least 28 mols of an oxyalkylene
per mol of phenol; (b) a monoalkylphenol adducted with
6 to 50 mols of an oxyalkylene per mol of ‘monoalkyl
F.l..
vise.
vise.
42
42
45
phenol, the alkyl group of the latter having from 4 to 14
10 carbon atoms; (0) a polyalkylphenol adducted with 12
to 50 mols of an oxyalkylene per mol of polyalkylphenol,
the alkyl groups of the latter each having at least one car
bon atom and together having from 3 to 28 carbon atoms;
(d) a mixture of a monoalkylphenol and polyalkylphenol
15 adducted with 2 to 4 weights of oxyalkylene per weight
of said mixture, the alkyl groups of the monoalkylphenol
and the polyalkylphenol each having 4 to 14 carbon atoms;
(e) a sulfonated alkylphenol-oxyalkylene adduct contain
ing 4 to 30 mols of oxyalkylene per mol of alkylphenol, the
OX-21i0: Nonylphenol adducted with 12 mols ethylene oxide.
0X-153 1:2: Still bottoms from nonylphenol process adducted with 2 20 alkyl groups of the alkylphenol containing 6 to 14 carbon
weights of ethylene oxide per weight of still bottoms.
atoms; and (f) a naphthenic acid adducted with 15 to 50
OX-191: N onylphenol adducted with 30 mols of ethylene oxide.
OX-438: Naphthenic acids adducted with 30 mols of ethylene oxide.
mols of oxyalkylene per mol of naphthenic acid, the lat
OX-490: Ortho-sec-butyl phenol adducted with 30 mols ethylene oxide.
ter having a molecular weight in the range of 300 to 350;
0X-518: Dodecyl phenol adducted with 12 mols ethylene oxide.
OX-52l: Naphthenic acids adducted with 12 mols ethylene oxide, the
said
oxyalkylene adducted with the selected surfactant
acigs being as identi?ed above, i.e. high molecular weight naphthenic 25
being selected from the groups consisting of oxyethylene
8C1 S.
OX-534: Ortho-sec-butyl phenol adducted with 12 mols ethylene oxide.
and oxypropylene and mixtures thereof.
FIB-2688: Dodecyl phenol adducted with 30 mols ethylene oxide.
2. The emulsion ?uid of claim 1 wherein said surfactant
Teox 120: Tall oil adducted with 12 mols ethylene oxide.
421mm. salt: sulfonated adduct of nonylphenol with 4 mols of ethylene
is nonylphenol adducted with 6 to 50 mols of said
0X1 e.
Tests using the preferred formula, anhydrite-saturated
oxyalkylene.
30
3. The emulsion ?uid of claim 1 wherein said surfactant
water containing 900 p.p.m. of Cl-, 15 lb./bbl. of shale
comprises a mixture of nonylphenol and dinonylphenol
but no oil resulted in total ?uid loss.
adducted with 2 to 4 weights of said oxyalkylene per
In Table X, there is shown a comparison of results ob~
weight of said mixture.
tained when using 12 and 30 mol. ethylene oxide adducts
4. The emulsion ?uid of claim 1 wherein said surfactant‘
of various phenolic materials. These results were ob 35 comprises a sulfonated nonylphenol-oxyalkylene adduct
tained using an emulsion comprising water saturated with
containing 4 to 30 mols of said oxyalkylene per mol of
anhydrite and containing 4% by weight of NaCl, 8% by
nonylphenol.
volume of diesel oil and 1 lb./bbl. of the indicated sur
5. The emulsion ?uid of claim 1 wherein said surfactant
factant. With regard to the ?gures under “Clay Toler
comprises a mixture of nonylphenol adducted with 6 to
40
ance,” the ?rst ?gure states the lbs./bbl. of clay the emul
50 mols of said oxyalkylene and nonylphenol still bottoms
sion could tolerate without the clay ?occing and the
adducted with about 2 weights of said oxyalkylene per
second ?gure is the lbs./bbl. of clay required to cause
Weight of said still bottoms, the latter comprising a mix
the clay to ?oc or the emulsion to break.
ture of nonylphenol and dinonylphenol.
6. An oil-in-water emulsion well drilling ?uid compris
TABLE X
as
Suriactant
Dinonylphenol plus 12 E0 1 _______ -.
Dinonylphenol plus 30 E.O.___
I
Sponta
neity
Good.-.
Dodecylphenol plus 12 13.0....
Dodecylphenol plus 30 E.O ____ _.
Paratert amylphenol plus 12 E0
Paratert amylphenol plus 30 E.O
Naphthenic acid plus 12 13.0
Naphthenic acid plus 30 E.O
Nonyl phenol plus 12 E.O_____
Nonyl phenol plus 30 E.0___._
o-Sec-butyl phenol plus 12 E.O__
o-Sec-butyl phenol plus 30 E.O__
p-Sec-butyl phenol plus 12 E.O_
p—Sec-butyl phenol plus 30 15.0..
di-Sec-butyl phenol plus 12 12.0.
di-Sec-butylphenol plus 30 13.0 ..... ..
1 E.O.—Ethylene oxide.
ing a minor amount of oil dispersed in a major amount
of water containing at least one of sodium chloride and
calcium sulfate, said emulsion containing and being sta
bilized by at least 0.5 pound per barrel of a phenol ad
ducted with at least 28 mols of an oxyalkylene selected
50
from the group consisting of oxyethylene and oxypropyl
one and mixtures thereof.
7. An oil-in-water emulsion well drilling ?uid compris
ing a minor amount of oil dispersed in a major amount
of water containing at least one of sodium chloride and
calcium sulfate, said emulsion containing and being sta
bilized by at least 0.5 pound per barrel of a monoalkyl
phenol adducted with 6 to 50 mols of oxyalkylene per
mol of monoalkylphenol, the alkyl group of the latter
having from 4 to 14 carbon atoms and said oxyalkylene
60 being selected from the group consisting of oxyethylene
and oxypropylene and mixtures thereof.
8. The emulsion ?uid of claim 7 wherein the ‘amount of
oxyalkylene adducted with said monoalkylphenol is se
lected to be in the upper part of said 6 to 50 mol range
hereinabove set forth, together with other advantages 65 when
the number of carbon atoms in said alkyl group is
which are obvious and which are inherent to the compo
selected
to be in the upper part of said 4 to 14 carbon
sition and process.
atom range and vice versa.
It will be understood that certain features and subcom
9. The emulsion ?uid of claim 7 wherein said mono
binations are of utility and may be employed without
alkylphenol is nonylphenol.
reference to other features and subcombinations. This is 70
10. An oil-in-water emulsion well drilling ?uid com
contemplated by and is within the scope of the claims.
prising a minor amount of oil dispersed in a major
From the foregoing it will be seen that this invention
is one well adapted to attain all of the ends and objects
The invention having been described, What is claimed
is:
amount of water containing at least one of sodium
chloride and calcium sulfate, said emulsion containing
1. An oil-in-water emulsion well drilling ?uid com
and being stabilized by at least 0.5 pound per barrel of
prising a minor amount of oil dispersed in a major 75 a polyalkylphenol adducted with 12 to 50 mols of oxy
3,062,740
25
26
valkylene per mol of polyalkylphenol, the alkyl groups
alkylphenol containing 6 to 14 carbon atoms; and (f)
of the latter having at least one carbon atom per group
and a total for all groups of 3 to 28 carbon atoms, said
alkylene per mol of naphthenic acid, the latter having
oxyalkylene being selected from the group consisting of
oxyethylene and oxypropylene and mixtures thereof.
a naphthenic acid adducted with 15 to 50 mols of oxy
a molecular weight in the range of 300‘ to 350; said
emulsion having the spontaneity with which it is formed
improved by having therein a second surfactant hav
inng a greater oil solubility than said ?rst surfactant, and
selected from the group consisting of: (a) a dialkyl
11. An oil-in-water emulsion well drilling ?uid com
prising a minor amount of oil dispersed in a major
amount of water containing at least one of sodium chlo
phenol adducted with from 10 to 14 mols of an oxy
ride and calcium sulfate, said emulsion containing and
being stabilized by at least 0.5 pound per barrel of a 10 alkylene per mol of dialkylphenol, the alkyl groups of
the latter each having at least one carbon atom and to
mixture of monoalkylphenol and polyalkylphenol ad
gether having from 3 to 28 carbon atoms; and (b) a
ducted with 2 to 4 Weights of .oxyalkylene per weight of
said mixture, the alkyl groups of the monoalkylphenol
and the polyalkylphen-ol each having 4 to 14 carbon
atoms, said oxyalkylene being selected from the group
consisting of oxyethylene and oxypropylene and mixtures
thereof.
12. The emulsion ?uid of claim 11 said mixture of
monoalkylphenol and polyalkylphenol is a still bottoms
derived by fractionating an alkylate product from a 20
phenol-alkylene alkylation step, said still bottoms contain
ing about 15 to 30 percent of said monoalkylphenol with
a major portion of the balance being dialkylphenol.
13. An oil-in-water emulsion well drilling ?uid com
prising a minor amount of oil dispersed in a major amount
of water containing at least one of sodium chloride and
calcium sulfate, said emulsion containing and being sta
bilized by at least 0.5 pound per barrel of a sulfonated
alkylphenol-oxyalkylene adduct containing 4 to 30 mols
of oxyalkylene per mol of alkylphenol, the alkyl group
containing 6 to 14 carbon atoms and the oxyalkylene be
ing selected from the group consisting of oxyethylene and
oxypropylene and mixtures thereof.
14. The emulsion ?uid of claim 13 wherein the amount
mixture of monoalkylphenol and dialkylphenol adducted
with 1 to 2 weights of oxyalkylene per weight of said
mixture, said mixture comprising a still bottoms derived
by fractionating an alkylate product from a phenol
alkylene ‘alkylation step, the still bottoms containing about
15 to 30 percent of said monoalkylphenol with a major
portion of the balance being dialkylphenol, the alkyl
groups of the monoalkylphenol and the dialkylphenol
each having 4 to 14 carbon atoms; said oxyalkylene
being selected from the group consisting of oxyethylene
and oxypropylene and mixtures thereof; said second
surfactant being present in an amount within the range
of '10 to 50 weight percent of the total weight of said
one and said second surfactants present in the ?uid.
19. The emulsion ?uid of claim 18 wherein said
surfactant for improving the spontaneity is said still hot
toms mixture adducted with about 2 weights of said oxy
alkylene per weight of said still bottoms mixture.
20. The emulsion ?uid of claim 19 wherein said still
bottoms mixture comprises nonylphenol and dinonyl
phenol.
21. An oil-in-water emulsion well drilling ?uid com
of oxyalkylene adducted with said alkylphenol is within 35 prising a minor portion of oil dispersed in a major por
the range of 4 to 12 mols of oxyalkylene per mol of
alkylphenol.
15. The emulsion ?uid of claim 14 wherein said alkyl
phenol is nonylphenol.
16. An oil-in-water emulsion well drilling ?uid com
prising a minor amount of oil dispersed in a major
amount of water containing at least one of sodium chlo
ride and calcium sulfate, said emulsion containing and
being stabilized by at least ‘0.5 pound per barrel of a
naphthenic acid adducted with 15 to 50 mols of oxy
alkylene per mol of naphthenic acid, the latter having a
molecular weight in the range of 300 to 350 and said
tion of water containing at least one of sodium chloride
and calcium sulfate, said emulsion containing and being
stabilized with a mixture of surfactants comprising: at
least ‘0.5 pound per barrel of a monoalkylphenol ad
ducted with 6 to 50 mols of oxyalkylene per mol of mono
alkylphenol, the alkyl group of the monoalkylphenol
having from 4 to 14 carbon atoms; and a mixture of
monoalkylphenol and dialkylphenol adducted with 1 to
2 weights of oxyalkylene per weight of said mono- and
dialkylphenol mixture, the latter comprising a still ‘bot
toms derived by fractionating an alkylate product from
oxyalkylene being selected from the group consisting of
oxyethylene and oxyp-ropylene and mixtures thereof.
a phenol-alkylene alkylation step; the alkyl groups of the
still bottoms mixture each having 4 to 14 carbon atoms;
said oxyalkylene being selected from the group consist
containing at least 1 percent by weight of sodium
chloride, said emulsion containing and being stabilized
nonylphenol.
17. The emulsion ?uid of claim 16 wherein said naph 50 ing of oxyethylene and oxypropylene and mixtures
thereof; the still bottoms adduct mixture being present
thenic acid has an acid number in the range of 160 ‘to
in an amount within the range of 10 to 50 weight per~
190.
cent of the total weight of the still bottoms adduct mix
18. An oil-in-water emulsion well drilling ?uid com
ture and the monoalkylphenol adduct.
prising a minor amount of oil dispersed in a major amount
22. The emulsion ?uid of claim 21 wherein said alkyl
of water substantially saturated with calcium. sulfate and 55
by a ?rst surfactant, comprising at least one vsurfactant
present in an amount of at least 0.5 pound per barrel
phenols are nonylphenol and said dialkylphenol is di
23. In a method of drilling a well through earthen
formations containing at least one of sodium chloride
and selected from the group consisting of: (a) phenol 60 and calcium sulfate, wherein a drilling ?uid is circu
lated through a drill string, the improvement which com
adducted with at least 28 mols of an oxyalkylene per
prises passing through the drill string and in contact with
mol of phenol; (b) a monoalkylphenol adducted with 6
said formations a drilling ?uid comprising an oil-in-water
to 50 mols of an oxyalkylene per mol of monoalkyl
emulsion of a minor amount of oil in a major amount
phenol, the alkyl group of the latter having from 4 to
14 carbon atoms; (0) a polyalkylphenol adducted with 65 of water stabilized by at least 0.5 pound per barrel of
a surfactant selected from the group consisting of: (a)
12 to 50 mols of an oxyalkylene per mol of polyalkyl
phenol adducted with at least 28 mols of an oxyalkylene
phenol, the alkyl groups of the latter each having at least
per mol of phenol; (b) a monoalkylphenol adducted
one carbon atom and together having from 3 to 28 car
with 6 to 50 mols of an oxyalkylene per mol of mono
bon ‘atoms; (d) a mixture of a monoalkylphenol and
polyalkylphenol adducted with 2 to 4 weights of oxy 70 alkylphenol, the alkyl group of the latter having from
4 to 14 carbon atoms; (0) a polyalkylphenol adducted
alkylene per weight of said mixture, the alkyl groups of
with 12 to 50 mols of an oxyalkylene per mol of poly
the monoalkylphenol and the polyalkylphenol each hav
alkylphenol, the alkyl groups of the latter each having
ing 4 to 14 carbon atoms; (a) a sulfonated alkylphenol
at
least one carbon atom and together having from 3 to
oxyalkylene adduct containing 4 to 30 mols of oxy
alkylene per mol of alkylphenol, the alkyl groups of the 75 28 carbon atoms; (d) a mixture of a monoalkylphenol
spear/lo
27
and polyalkylphenol adducted with 2 to 4 weights of oxy
28
group consisting of: (a) phenol adducted with at least
alkylene per weight of said mixture, the alkyl groups
of the monoalkylphenol and polyalkylphenol each hav
ing 4 to 14 carbon atoms; (2) a sulfonated alkylphenol
oxyalkylene adduct containing 4 to 30' mols of oxyalkyl
ene per mol of alkylphenol, the alkyl group of the alkyl
phenol containing 6 to 14 carbon atoms; and (f) a
of the latter having from 4 to 14 carbon atoms; (0) a
polyalkylphenol adducted with 12 to 5-0 mols of an oxy
alkylene per mol of polyalkylphenol, the alkyl groups of
naphthenic acid adducted with 15 to 50 mols of oxy
the latter each having at least one carbon atom and to
alkylene per mol of naphthenic acid, the latter having a
28 mols of an oxyalkylene per mol of phenol; (b) a
monoalkylphenol adducted with 6 to 50 mols of an oxy
alkylene per mol of monoalkylphenol, the alkyl group
gether having from 3 to 28 carbon atoms; (d) a mix
molecular weight in the range of 300 to 350; said ox‘ 10 ture of a monoalkylphenol and polyalkylphenol ad
alkylene adducted with the selected surfactant being se
ducted with 2 to 4 weights of oxyalkylene per weight
lected from the group consisting of oxyethylene and
of said mixture, the alkyl groups of the monoalkylphenol
oxypropylene and mixtures thereof, said emulsion hav
and the polyalkylphenol each having 4 to 14 carbon
ing been formed and stabilized before any substantial
atoms; (2) a sulfonated alkylphenol-oxyalkylene adduct
quantity of clay or shale is suspended therein by virtue
containing 4 to 30 mols of oxyalkylcne per mol of alkyl
of the drilling operation.
phenol, the alkyl groups of the alkylphenol containing
24. The method of claim 23 wherein said surfactant
is nonylphenol adducted with 6 to 50 mols of said oxy
6 to 14 carbon atoms; and (f) a naphthenic acid ad
ducted with 15 to 50'mols of oxyalkylene per mol of
alkylene.
naphthenic acid, the latter having a molecular weight in
25. The method of claim 23 wherein said surfactant 20 the range of 300 to 350; said oxyalkylene adducted with
comp-rises a mixture of nonylphenol and clinonylphenol
the selected surfactant being selected from the groups
adducted with 2 to 4 weights of said oxyalkylene per
consisting of oxyethylene and oxypropylene and mix
weight of said mixture.
tures thereof.
26. The method of claim 23 wherein said surfactant
30. The method of reducing the ?uid loss of a water
comprises a sulfonated nonylphenol-oxyalkylene adduct 25 base mud containing earthen materials therein and also
containing 4 to 30 mols of said oxyalkylene per mol
containing at least one of sodium chloride and calcium
of nonylphenol.
sulfate which comprises adding 5 to 50 volume percent
27. The method of claim 23 wherein said surfactant
of hydrocarbon oil to the base mud along with at least
comprises a mixture of nonylphenol adducted with 6 to
0.5 lb./bbl. of a surfactant consisting of nonylphenol
50 mols of said oxyalkylene and nonylphenol still bot 30 adducted with 12 to 50 mols of oxyethylene.
toms adducted with about 2 weights of said oxyalkylene
31. The method of reducing the ?uid loss of a water
per weight of said still bottoms, the latter comprising
'base mud containing earthen materials therein and also
a mixture of nonylphenol and dinonylphenol.
containing at least one of sodium chloride and calcium
28. In a method of drilling a well through earthen
sulfate which comprises adding 5 to 50 volume percent
formations containing. at least one of sodium chloride 35 of hydrocarbon oil to the base mud along with at least
and calcium sulfate wherein a drilling ?uid is circulated
0.5 lb./bbl. of a surfactant consisting of a mixture of
through a drill string, the improvement which comprises
nonylphenol and dinonylphenol adducted with 2 to 4
passing through the drill string and in contact with said
formations a drilling ?uid comprising an oil-in-water
weights of oxyethylene per weight of said mixture.
32. The method of reducing the ?uid loss of a water
emulsion of a minor amount of oil in a major amount
of water stabilized by a mixture of surfactants com
base mud containing earthen materials therein and also
prising: at least ‘0.5 pound per barrel of a monoalkyl
phenol adducted with 6 to 50 mols of oxyalkylene per
mol of monoalkylphenol, the alkyl group of the mono
alkylphenol having from 4 to 14 carbon atoms; and a
sulfate which comprises adding 5 to 50 volume percent
of hydrocarbon oil to the base mud along with at least
0.5 lb./bbl. of a surfactant consisting of a naphthenic
mixture of monoalkylphenol and dialkylphenol adducted
with 1 to 2 weights of oxyalkylene per weight of said
mono- and dialkylphenol mixture, the latter comprising
a still bottoms derived by fractionating an alkylate prod
uct from a phenolalkylene alkylation step; the alkyl
groups of the still bottoms mixture each having 4 to 14
carbon atoms; said oxyalkylene being selected from the
group consisting of oxyethylene and oxypropylene, and
mixtures thereof, the still bottoms adduct mixture being
present in an amount within the range of 10 to 50 weight
percent of the total weight of the still bottoms adduct
mixture and the monoalkylphenol adduct; said emulsion
having been formed and stabilized before any substantial
quantity of clay or shale is suspended therein by virtue
of the drilling operation.
29. The method of reducing the ?uid loss of a water
base mud containing earthen materials therein and also
containing at least one of sodium chloride and calcium
sulfate which comprises adding 5 to 50 volume percent
of hydrocarbon oil to the base mud along with at least
0.5 pound per barrel of a surfactant selected from the
containing at least one of sodium chloride and calcium
' acid adducted with about 30 mols of oxyethylene.
33. The method of reducing the ?uid loss of a water
base mud containing earthen materials therein and also
containing at least one of sodium chloride and calcium
sulfate which comprises adding 5 to 50 volume percent
of hydrocarbon oil to the base mud along with at least
0.5 lb./bbl. of a surfactant consisting of dodecylphenol
adducted with 12 to 50 mols of oxyethylene.
References {Iited in the ?le of this patent
UNITED STATES PATENTS
2,423,144
2,509,588
2,555,794
2,564,753
2,593,112
2,689,219
Greg _______________ __ July 1,
Dawson _____________ __ May 30,
Henkes ______________ __ June 5,
Cox ________________ __ Aug. 21,
Cross et a1. __________ __ Apr. 15,
Menaul ______________ __ Sept. 14,
1947
1950
1951
1951
1952
1954
OTHER REFERENCES
Antarox A-200, pub. by General Aniline and Film
Corp., N.Y., March 3, 1950, pages 2 to 5.
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